CN111097405B - Process for catalytic oxidation of cyclic hydrocarbons - Google Patents
Process for catalytic oxidation of cyclic hydrocarbons Download PDFInfo
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- CN111097405B CN111097405B CN201811269829.6A CN201811269829A CN111097405B CN 111097405 B CN111097405 B CN 111097405B CN 201811269829 A CN201811269829 A CN 201811269829A CN 111097405 B CN111097405 B CN 111097405B
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Abstract
The present disclosure relates to a process for the catalytic oxidation of a cyclic hydrocarbon, the process comprising: contacting a cyclic hydrocarbon with an oxidant in the presence of a catalyst to perform an oxidation reaction, wherein the catalyst contains BiVO 4 A composite of quantum dots and carbon dots. The present disclosure employs a composition comprising BiVO 4 Catalysis of composite material of quantum dots and carbon dots as catalystThe oxidation reaction of the cyclic hydrocarbon can realize the selective oxidation of the cyclic hydrocarbon under mild conditions, the conversion rate of the raw material is high, and the selectivity of the target product is optimized.
Description
Technical Field
The present disclosure relates to a process for the catalytic oxidation of cyclic hydrocarbons.
Background
Carbon-based materials include carbon nanotubes, activated carbon, graphite, graphene, fullerenes, carbon nanofibers, nanodiamonds, and the like. Scientific research on nanocarbon catalysis began in the 90's of the last century. Researches show that the surface chemical properties of the nano-carbon material (mainly carbon nano-tubes and graphene) can be flexibly regulated, and saturated and unsaturated functional groups containing heteroatoms such as oxygen, nitrogen and the like can be modified on the surface of the nano-carbon material, so that the nano-carbon material has certain acid-base properties and redox capability, and can be directly used as a catalyst material. Researches and develops new catalytic materials related to fullerene (carbon nano tube), widens the application of the new catalytic materials in the fields of petrochemical industry, fine chemical industry and the like, and has profound theoretical significance and huge potential application prospect.
Metal organic framework compounds have attracted considerable attention over the last two decades as a new type of porous crystalline material due to their high specific surface area, adjustable pore structure and controllable structure. By regulating the metal ions or clusters and the organic ligands, different functionalized metal organic framework compounds can be formed with strong chemical bonds. Recently, metal organic framework compounds have been identified as a very promising candidate for the synthesis of carbon-based materials. However, the metal-organic framework compounds have the disadvantage of relatively low thermal and chemical stability, and therefore, how to convert the metal-organic framework compounds into carbon-based materials with good catalytic activity still faces a great challenge.
Epoxidation of olefins is currently an important route for numerous chemical production and industrial applications. For example, the selective oxidation of cis-cyclooctene for use in the synthesis of pharmaceuticals, pesticides, and polyesters. The selective oxidation of cis-cyclooctene is often difficult, particularly under catalytic conditions, because the oxidation product of cis-cyclooctene is not a single product, with possible products including cyclooctane, 2-cyclooctenone and 1, 2-cyclooctadiene. In order to develop a catalytic system, various methods for the selective epoxidation of cis-cyclooctene have been reported. However, designing a highly selective, high yield catalyst in a process for the catalytic oxidation of cis-cyclooctene remains a significant challenge. In addition to the epoxidation of cycloolefins, cyclic ketones and alcohols obtained by catalytic oxidation of cycloalkanes are also important chemical raw materials, for example, cyclohexanone and cyclohexanol are used in the preparation of adipic acid, caprolactam, plasticizers, detergents and the like, and also in the preparation of solvents and emulsifiers. Therefore, the research of a process which has high conversion rate of naphthenic hydrocarbon (especially cyclohexane), good selectivity of naphthenic hydroperoxide (further decomposing into cyclic ketone and cyclic alcohol) and is environment-friendly and simple has very important practical significance.
Disclosure of Invention
The present disclosure is directed to a method for catalytic oxidation of cyclic hydrocarbons using a catalyst having excellent catalytic performance for selective oxidation of cyclic hydrocarbons under milder conditions.
In order to achieve the above object, the present disclosure provides a method for catalytic oxidation of cyclic hydrocarbons, the method comprising: contacting a cyclic hydrocarbon with an oxidant in the presence of a catalyst to perform an oxidation reaction, wherein the catalyst contains BiVO 4 A composite of quantum dots and carbon dots.
Optionally, the BiVO is based on the total weight of the composite material 4 The content of the quantum dots is 20 to 75 wt%, preferably 30 to 70 wt%; the content of the carbon dots is 25 to 80% by weight, preferably 30 to 70% by weight.
Optionally, the carbon dots are graphene quantum dots, carbon nanodots, or polymer dots.
Optionally, the particle size of the composite material is 2 to 15nm, preferably 3 to 12nm, and more preferably 5 to 10nm.
Optionally, the step of preparing the composite material comprises:
(1) Respectively providing a solution A and a solution B, wherein the solution A is a solution containing a soluble anionic surfactant and a soluble salt of metal Bi, and the solution B is a solution containing a compound of metal V;
(2) Mixing the solution A and the solution B obtained in the step (1) under the condition of stirring to obtain a mixture;
(3) Carrying out hydrothermal reaction on the mixture obtained in the step (2) to obtain a hydrothermal reaction product;
(4) And (4) uniformly mixing the hydrothermal reaction product obtained in the step (3) with the carbon dots, collecting a solid product, and washing and drying the solid product.
Optionally, in the step (1), the molar ratio of the metal V compound to the soluble anionic surfactant to the metal Bi soluble salt is (0.5-3): (0.5-5): 1, preferably (1 to 3): (2-4): 1;
the soluble salt of the metal Bi is bismuth chloride, bismuth nitrate or bismuth sulfate; the soluble anionic surfactant is sodium oleate, sodium alkyl sulfonate, sodium alkyl aryl sulfonate, sodium alkyl sulfate or secondary sodium alkyl sulfate; the compound of the metal V is vanadate or vanadate.
Optionally, in step (2), the stirring conditions include: the stirring speed is 100-5000 r/min, and the time is 0.5-6 h;
preferably, the stirring conditions include: the stirring speed is 800-2000 r/min, and the time is 1-4 h.
Alternatively, in step (3), the hydrothermal reaction comprises: and carrying out a first hydrothermal reaction on the mixture at 100-200 ℃ for 1-48 h, and then carrying out a second hydrothermal reaction at 160-250 ℃ for 1-24 h.
Optionally, in step (4), the weight ratio of the carbon point to the hydrothermal reaction product is 1: (0.2 to 10), preferably 1: (0.5 to 5);
the mixing is carried out under agitation conditions comprising: the stirring speed is 100-5000 r/min, and the stirring time is 0.1-12 h;
the drying conditions include: the temperature is 20-150 ℃.
Optionally, the oxidation reaction is carried out in a slurry bed reactor, and the amount of the catalyst is 20 to 100mg, preferably 40 to 60mg, based on 10mL of the cyclic hydrocarbon.
Optionally, the oxidation reaction is carried out in a fixed bed reactor, and the weight hourly space velocity of the cyclic hydrocarbon is 0.01-100 h -1 Preferably 0.1 to 10 hours -1 。
Optionally, the molar ratio of the cyclic hydrocarbon to the oxidant is 1: (0.1 to 10), preferably 1: (0.2 to 5);
the oxidant is hydrogen peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, ethylbenzene hydroperoxide or peroxypropionic acid, preferably hydrogen peroxide.
Optionally, the cyclic hydrocarbon includes cycloolefins and cycloalkanes;
the cycloolefin is one selected from C3-C8 cyclomonoolefin and C6-C8 cyclodiolefin, preferably one selected from C3-C8 cyclomonoolefin, and more preferably cyclooctene;
the cycloalkane is one selected from C3-C8 cycloalkanes, preferably one selected from cyclohexane, cyclopentane, alkyl-substituted cyclohexane, alkyl-substituted cyclopentane, halogen-substituted cyclohexane and halogen-substituted cyclopentane, and more preferably cyclohexane.
Optionally, the oxidation reaction conditions are: the temperature is 50-100 ℃, and preferably 60-80 ℃; the time is 4 to 72 hours, preferably 6 to 48 hours; the pressure is 0 to 20MPa, preferably 0 to 10MPa.
Through the technical scheme, the method adopts the structure containing BiVO 4 The composite material of the quantum dots and the carbon dots is used as a catalyst to catalyze the oxidation reaction of the cyclic hydrocarbon, so that the selective oxidation of the cyclic hydrocarbon can be realized under mild conditions, the conversion rate of raw materials is high, and the selectivity of a target product is optimized.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a process for the catalytic oxidation of a cyclic hydrocarbon, the process comprising: contacting a cyclic hydrocarbon with an oxidant in the presence of a catalyst to perform an oxidation reaction, wherein the catalyst contains BiVO 4 A composite of quantum dots and carbon dots.
The present disclosure employs a composition comprising BiVO 4 The composite material of the quantum dots and the carbon dots is used as a catalyst to catalyze the oxidation reaction of the cyclic hydrocarbon, can realize the selective oxidation of the cyclic hydrocarbon under mild conditions, and has high conversion rate of raw materials and high selectivity of target products.
According to the disclosure, the composition contains BiVO 4 The composite material of the quantum dots and the carbon dots has excellent catalytic performance on the selective oxidation of cyclic hydrocarbons such as cis-cyclooctene or cyclohexane under mild conditions. To better achieve the objects of the present disclosure, the BiVO is based on the total weight of the composite material 4 The content of the quantum dots is 20 to 75 weight percent, and preferably 30 to 70 weight percent; the content of the carbon dots is 25 to 80% by weight, preferably 30 to 70% by weight.
Quantum dots, according to the present disclosure, are semiconductor nanostructured materials that confine excitons in three spatial directions, no dimension in three dimensions greater than twice the exciton bohr radius of their corresponding semiconductor material. In this disclosure, said BiVO 4 The particle size of the quantum dots is generally 1 to10nm, preferably 2 to 8nm.
According to the present disclosure, the Carbon Dots (CDs) refer to carbon particles having fluorescent properties with a size of less than 20 nm. The chemical structure of the carbon dots can be a hybrid carbon structure of sp2 and sp3, a single-layer or multi-layer graphite structure, and polymer aggregate particles. The carbon dots mainly comprise graphene quantum dots, carbon nanodots and polymer dots. The graphene quantum dots refer to a carbon core structure with a single layer or less than 5 layers of graphene and chemical groups bonded at edges. The size of the graphene quantum dots has a typical anisotropy, the transverse dimension is larger than the height of the longitudinal direction, and the graphene quantum dots have a typical carbon lattice structure. Graphene quantum dots are a class of materials that physicists use to study the photoelectric band gap of graphene, and typically require electron beam etching of large sheets of graphene. The carbon nanodots are generally spherical structures, and may be classified into lattice-distinct carbon nanodots and lattice-free carbon nanodots. Due to the diversity of the carbon nano-dot structure, the carbon nano-dot luminescent centers prepared in different modes and the luminescent mechanism have great difference. Specifically, it can be classified into carbon quantum dots having distinct lattices and carbon nanodots having/not having lattices. The carbon quantum dots with obvious crystal lattices have obvious quantum size dependence, and the optimal fluorescence emission peak is red-shifted along with the size change from small to large. The lattice-free carbon nano-dots have no quantum size effect, the luminescent centers of the lattice-free carbon nano-dots are not completely controlled by the carbon cores, and the surface groups have non-negligible influence on luminescence. The polymer dots are typically cross-linked flexible aggregates formed from a non-conjugated polymer by dehydration or partial carbonization, with no carbon lattice structure present. Polymer dots are a class of materials from which carbon dots extend. The polymer dots comprise fluorescent polymer dots formed by moderately crosslinking or carbonizing non-conjugated macromolecules and fluorescent polymer dots formed by assembling carbon cores and polymers.
Methods for preparing the carbon dots are well known to those skilled in the art in light of this disclosure. The raw material source of the carbon dots can generally comprise an inorganic carbon source and an organic carbon source. The specific preparation method can comprise methods such as an arc discharge method, a laser ablation/passivation method, an electrochemical method, a pyrolysis method, a field-assisted method and the like. The carbon dots can be prepared in one step by a high temperature pyrolysis method, usually using citrate as a carbon source or using citric acid and glutathione together as a carbon source.
According to the present disclosure, the carbon dots are preferably graphene quantum dots, carbon nanodots or polymer dots, and the carbon dots are commercially available or can be prepared by methods known in the art. The particle size of the carbon dots is generally 2 to 8nm, preferably 3 to 6nm.
According to the present disclosure, the particle size of the composite material may be 2 to 15nm, preferably 3 to 12nm, and more preferably 5 to 10nm. In the present disclosure, the particle size refers to the maximum three-dimensional length of the particle, i.e., the maximum distance between two points on the particle.
According to the present disclosure, the preparing step of the composite material may include:
(1) Respectively providing a solution A and a solution B, wherein the solution A is a solution containing a soluble anionic surfactant and a soluble salt of metal Bi, and the solution B is a solution containing a compound of metal V;
(2) Mixing the solution A and the solution B obtained in the step (1) under the condition of stirring to obtain a mixture;
(3) Carrying out hydrothermal reaction on the mixture obtained in the step (2) to obtain a hydrothermal reaction product;
(4) And (4) uniformly mixing the hydrothermal reaction product obtained in the step (3) with the carbon dots, collecting a solid product, washing and drying.
According to the present disclosure, in the preparation step of the composite material, in the step (1), the molar ratio of the compound of the metal V, the soluble anionic surfactant and the soluble salt of the metal Bi may be (0.5 to 3): (0.5-5): 1, preferably (1 to 3): (2-4): 1. the soluble salt of the metal Bi can be bismuth chloride, bismuth nitrate or bismuth sulfate. The soluble anionic surfactant is preferably a sodium salt type anionic surfactant, and may be, for example, sodium oleate, sodium alkylsulfonate, sodium alkylarylsulfonate, sodium alkylsulfate or secondary sodium alkylsulfate, preferably sodium oleate. The solution a is generally an aqueous solution containing a soluble anionic surfactant and a soluble salt of metal Bi, and the amount of the solvent water in the solution a is not particularly limited as long as the soluble anionic surfactant and the soluble salt of metal Bi can be sufficiently dissolved. The solvent in the solution containing the metal V compound may be an inorganic solvent or an organic solvent. The compound of the metal V may be a vanadate or vanadate. When the compound of metal V is vanadate, the solution is generally aqueous solution, that is, the solvent is water, and when the compound of metal V is vanadate, the solution is generally alcoholic solution, for example, the solvent in solution B can be at least one of ethanol, isopropanol, n-hexanol and tert-butanol. That is, the solution B is an aqueous solution or an alcoholic solution of the compound containing the metal V, and the amount of the solvent (water or alcohol) in the solution B is not particularly limited as long as the compound containing the metal V can be sufficiently dissolved. In particular cases, in order to dissolve and disperse various solutes in the solution a or the solution B well in the solution to make the contact effect better, additional solvent may be added as needed to promote dissolution and dispersion of the metal salt in the solution.
According to the present disclosure, in the preparation step of the composite material, in the step (2), in order to make the mixing more sufficient after the solution B is added to the solution a, the mixing is performed under stirring conditions, which may include: the stirring speed is 100-5000 r/min, and the stirring time is 0.5-6 h; preferably, the stirring speed is 800 to 2000 rpm and the time is 1 to 4 hours.
According to the present disclosure, in the preparation step of the composite material, in step (3), in order to make the hydrothermal reaction more sufficient, the hydrothermal reaction may include: and carrying out a first hydrothermal reaction on the mixture at 100-200 ℃ for 1-48 h, and then carrying out a second hydrothermal reaction at 160-250 ℃ for 1-24 h. The hydrothermal reaction may be carried out in a conventional reactor, for example in a polytetrafluoroethylene reaction vessel. The pressure of the hydrothermal reaction process is not particularly limited, and may be the autogenous pressure of the system, or may be under an additional applied pressure condition, and preferably, the hydrothermal reaction process is performed under the autogenous pressure (generally, in a closed vessel).
According to the disclosure, in the step of preparing the composite material, in the step (4), the carbon dots are used in such an amount that the BiVO is present in the prepared composite material based on the total weight of the composite material 4 The content of the quantum dots is 20 to 75 wt%, preferably 30 to 70 wt%; the content of the carbon dots is 25 to 80% by weight, preferably 30 to 70% by weight. For example, the weight ratio of the carbon dots to the hydrothermal reaction product may be 1: (0.2 to 10), preferably 1: (0.5-5). In order to mix the hydrothermal reaction product and the carbon dots uniformly, the mixing is preferably performed under stirring conditions including: the stirring speed is 100-5000 r/min, and the time is 0.1-12 h. The hydrothermal reaction product and the carbon dots are uniformly mixed and then the solid product is collected by a conventional method, such as filtration, centrifugation, and the like. The solid product is washed before drying, usually by rinsing, preferably with cyclohexane and/or absolute alcohol. The drying may be carried out at a temperature of 20 to 150 ℃, the drying time may be selected depending on the drying temperature, and may be generally 2 to 12 hours, and the drying may be carried out under normal pressure or under reduced pressure.
The process for the catalytic oxidation of cyclic hydrocarbons of the present disclosure may be carried out in various conventional catalytic reactors, for example, may be carried out in a batch tank reactor or a three-neck flask, or in suitable other reactors such as fixed bed, moving bed, suspended bed, and the like.
In an alternative embodiment of the present disclosure, the oxidation reaction may be carried out in a slurry bed reactor. In this case, the amount of the catalyst to be used may be appropriately selected depending on the amounts of the cyclic hydrocarbon and the oxidizing agent, and for example, the amount of the catalyst to be used may be 20 to 100mg, preferably 40 to 60mg, based on 10mL of the cyclic hydrocarbon.
In another alternative embodiment of the present disclosure, the oxidation reaction may be carried out in a fixed bed reactor. In this case, the weight hourly space velocity of the cyclic hydrocarbon may be, for example, 0.01 to 100 hours -1 Preferably 0.1 to 10 hours -1 。
In accordance with the present disclosure, to achieve the desired effect, the molar ratio of the cyclic hydrocarbon to the oxidant may be 1: (0.1 to 10), preferably 1: (0.2-5). The oxidizing agent may be an oxidizing agent conventionally used in the art, for example, the oxidizing agent may be hydrogen peroxide, t-butyl hydroperoxide, cumyl hydroperoxide, ethylbenzene hydroperoxide or peroxypropionic acid, and preferably, the oxidizing agent is hydrogen peroxide. The hydrogen peroxide is usually used in the form of an aqueous hydrogen peroxide solution, and the concentration of the aqueous solution is not particularly limited, and may be, for example, a 30 wt% aqueous hydrogen peroxide solution or the like.
According to the present disclosure, the cyclic hydrocarbon may include cycloolefins and cycloalkanes. Further, the cyclic olefin may be one selected from C3 to C8 cyclic monoolefins and C6 to C8 cyclic diolefins, preferably one selected from C3 to C8 cyclic monoolefins, more preferably cyclooctene; the cycloalkane may be a C3-C8 cycloalkane, and is preferably one selected from the group consisting of cyclohexane, cyclopentane, alkyl-substituted cyclohexane, alkyl-substituted cyclopentane, halogen-substituted cyclohexane and halogen-substituted cyclopentane, and more preferably cyclohexane.
According to the present disclosure, the conditions of the oxidation reaction may be: the temperature is 50-100 ℃, and preferably 60-80 ℃; the time is 4 to 72 hours, preferably 6 to 48 hours; the pressure is 0 to 20MPa, preferably 0 to 10MPa. In order to make the reaction more sufficient, it is preferable that the contact reaction is carried out under stirring.
The present disclosure is described in detail below with reference to examples, but the scope of the present disclosure is not limited thereby.
Preparation examples 1 to 4 are illustrative of the BiVO-containing compositions employed in the methods of the present disclosure 4 A composite of quantum dots and carbon dots and a method of preparing the same, a comparative preparation, are prepared to illustrate a catalytic material different from the present disclosure.
The following preparation examples:
carbon dots (CDs for short) reference method Science, VOL 347 970-974 (www.science mag.org/content/347/6225/970/suppl/DC 1) was prepared to obtain carbon dots CDs with a particle size of about 5nm.
The particle size of the composite material, the particle size of the quantum dots and the average particle size of the carbon dots are measured by TEM, and 20 particles are randomly selected from a TEM photograph, and the average particle size is calculated. The method for measuring the content of the carbon dots and the quantum dots in the composite material comprises the steps of calculating the weight of the quantum dots according to the amount of the metal oxide remaining after roasting at 350 ℃ for 3 hours (the heating rate is 2 ℃/min) in an air atmosphere, and then calculating the weight of the quantum dots by subtracting the weight of the quantum dots from the total weight of the composite material to obtain the weight of the carbon dots.
Preparation of example 1
Sodium oleate (1.3 mmol) and Bi (NO) 3 ) 3 ·5H 2 O (0.4 mmol), successively dissolved in 20mL of deionized water, formed solution A. Mixing Na 3 VO 4 ·12H 2 O (0.4 mmol) was dissolved in 20mL of deionized water to form solution B. Then, solution B was added to solution A and stirred vigorously for 2h (stirring speed 1200 rpm). Transferring the obtained mixture into a polytetrafluoroethylene kettle, sealing, carrying out first hydrothermal reaction at 100 ℃ for 12h, and then carrying out second hydrothermal reaction at 160 ℃ for 2h to obtain a hydrothermal reaction product (namely BiVO) 4 Quantum dot), sampling and measuring prepared BiVO 4 The average particle size of the quantum dots is 5nm. 0.2g of CDs solid is weighed and slowly added into the hydrothermal reaction product (the weight ratio of the CDs to the hydrothermal reaction product is 1.8), the mixture is stirred for 12 hours under the stirring speed of 800 revolutions per minute, then the solid product is collected by centrifugation, the collected solid product is washed by cyclohexane for 30 minutes, the temperature is raised to 85 ℃ to evaporate and volatilize the cyclohexane, and the obtained solid product is the CDs/BiVO 4 QDs composite particles A1, with an average particle size of about 7nm, wherein BiVO 4 The QDs content was 67 wt% and the CDs content was 33 wt%.
Preparation of example 2
A composite material was prepared according to the method of preparative example 1 except that during the synthesis the weight ratio of CDs to hydrothermal reaction product was 1:0.2, obtaining CDs/BiVO 4 QDs composite particles A2 having a mean particle size of about 8nm, wherein BiVO 4 The content of QDs is 20% by weight,the CDs content was 80% by weight.
Preparation of example 3
A composite material was prepared according to the method of preparation example 1 except that, during the synthesis, na was used 3 VO 4 ·12H 2 O, sodium oleate and Bi (NO) 3 ) 3 ·5H 2 The molar ratio of O is 0.5:0.5:1, obtaining CDs/BiVO 4 QDs composite particles A3 having a particle average size of about 12nm, wherein BiVO 4 The QDs content was 72 wt% and the CDs content was 28 wt%.
Preparation of example 4
A composite material was prepared according to the method of preparation example 1, except that sodium oleate was replaced by the same amount of sodium dodecylbenzenesulfonate to obtain CDs/BiVO 4 QDs composite particles A4 having an average particle size of about 14nm, wherein BiVO 4 The QDs content was 85 wt% and the CDs content was 15 wt%.
Preparation of comparative example 1
BiVO was prepared according to the method of example 1 4 QDs, after which no CDs solids were added. The method comprises the following specific steps: sodium oleate (1.3 mmol) and Bi (NO) 3 ) 3 ·5H 2 O (0.4 mmol), successively dissolved in 20mL of deionized water, formed solution A. Mixing Na 3 VO 4 ·12H 2 O (0.4 mmol) was dissolved in 20mL of deionized water to form solution B. Then, solution B was added to solution A and stirred vigorously for 2h (stirring speed 1200 rpm). Transferring the obtained mixture into a polytetrafluoroethylene kettle, sealing, preserving heat at 100 ℃ for 12 hours to perform a first hydrothermal reaction, preserving heat at 160 ℃ for 2 hours to perform a second hydrothermal reaction, collecting a solid product through centrifugation, washing the collected solid product with cyclohexane for 30 minutes, raising the temperature to 85 ℃ to evaporate and volatilize the cyclohexane, and obtaining a solid product, namely BiVO 4 QDs, noted D1, have a particle size of about 5nm.
Examples 1 to 8 illustrate the use of a catalyst containing BiVO 4 A method for catalyzing and oxidizing cyclooctene by using a composite material of quantum dots and carbon dots. Comparative examples 1 to 3 are intended to illustrate the process of catalytic oxidation of cyclooctene using a catalytic material different from that of the present disclosure.
In the following examples and comparative examples, the oxidation products were analyzed by gas chromatography (GC: agilent, 7890A) and gas chromatography-mass spectrometer (GC-MS: thermo Fisher Trace ISQ). Conditions of gas chromatography: nitrogen carrier gas, temperature programmed at 140K: 60 ℃,1 minute, 15 ℃/minute, 180 ℃,15 minutes; split ratio, 10:1; the injection port temperature is 300 ℃; detector temperature, 300 ℃. On the basis, the following formulas are respectively adopted to calculate the conversion rate of the raw materials and the selectivity of the target product:
percent cyclooctene conversion = (molar amount of cyclooctene added before reaction-molar amount of cyclooctene remaining after reaction)/molar amount of cyclooctene added before reaction × 100%;
selectivity% for epoxycyclooctane (= (molar amount of epoxycyclooctane formed after reaction)/molar amount of cyclooctene added before reaction × 100%.
Example 1
50mg of the composite particles A1 as a catalyst and 10mL of cis-cyclooctene were charged into a 50mL round-bottomed flask having a water condenser, followed by addition of 30% by weight of an aqueous hydrogen peroxide solution (molar ratio of hydrogen peroxide to cyclooctene: 2: 1), and after stirring the mixture at 80 ℃ under normal pressure for 8 hours, the catalyst was separated by centrifugation and filtration, and the results of analysis of oxidized products are shown in Table 1.
Examples 2 to 4
Cyclooctene was catalytically oxidized by the method of example 1, except that A1 was replaced with the same amounts of the composite particles A2 to A4, respectively. The results of the oxidation product analysis are shown in Table 1.
Example 5
60mg of the composite particles A1 as a catalyst and 10mL of cis-cyclooctene were charged into a 50mL round-bottom flask having a water condenser, then 30% by weight of aqueous hydrogen peroxide (molar ratio of hydrogen peroxide to cyclooctene is 4: 1) was added, and after stirring the mixture at 80 ℃ under normal pressure for 8 hours, the catalyst was separated by centrifugation and filtration, and the results of analysis of oxidized products are shown in Table 1.
Example 6
20mg of the composite particle A1 as a catalyst and 10mL of cis-cyclooctene were charged into a 50mL round-bottom flask having a water condenser, followed by addition of 30% by weight of aqueous hydrogen peroxide (molar ratio of hydrogen peroxide to cyclooctene is 2: 1), and after stirring the mixture at 60 ℃ under normal pressure for 8 hours, the catalyst was separated by centrifugation and filtration, and the results of analysis of oxidized products are shown in Table 1.
Example 7
80mg of the composite particles A1 as a catalyst and 10mL of cis-cyclooctene were charged into a 50mL round-bottom flask having a water condenser, followed by addition of 30% by weight of aqueous hydrogen peroxide (molar ratio of hydrogen peroxide to cyclooctene is 2 1), and after stirring the mixture at 80 ℃ under normal pressure for 4 hours, the catalyst was separated by centrifugation and filtration, and the results of analysis of oxidized products are shown in Table 1.
Example 8
50mg of the composite material particles A1 as a catalyst were loaded in a fixed bed reactor, cis-cyclooctene and 30 wt% aqueous hydrogen peroxide were fed into the reactor, and the weight hourly space velocity of cyclooctene was 5 hours -1 The results of the analysis of the oxidation products after 8 hours of reaction at 80 ℃ and 2MPa are shown in Table 1.
Comparative example 1
Cyclooctene was catalytically oxidized according to the procedure of example 1, except that the same amount of D1 (BiVO) was used 4 QDs) instead of the composite particles A1. The results of the oxidation products are shown in Table 1.
Comparative example 2
Cyclooctene was catalytically oxidized according to the method of example 1, except that the same amount of carbon dots CDs were used instead of the composite particles A1. The results of the oxidation products are shown in Table 1.
Comparative example 3
Cyclooctene was catalytically oxidized according to the procedure of example 1, except that the composite particles A1 were not used, i.e., the reaction was carried out in the absence of a catalyst. The results of the oxidation products are shown in Table 1.
TABLE 1
| Sources of catalyst | Cyclooctene conversion% | Selectivity to epoxycyclooctane% |
| Example 1 | 31 | 84 |
| Example 2 | 28 | 81 |
| Example 3 | 25 | 78 |
| Example 4 | 23 | 76 |
| Example 5 | 30 | 83 |
| Example 6 | 26 | 80 |
| Example 7 | 24 | 78 |
| Example 8 | 32 | 86 |
| Comparative example 1 | 6 | 11 |
| Comparative example 2 | 13 | 28 |
| Comparative example 3 | 10 | 36 |
As can be seen from Table 1, the use of a catalyst containing BiVO 4 The composite material of the quantum dots and the carbon dots can be used as a catalyst to realize the selective oxidation of cyclooctene under mild conditions, and the conversion rate of raw materials and the selectivity of target products are higher.
Examples 9 to 16 illustrate the use of a catalyst containing BiVO 4 A method for catalytic oxidation of cyclohexane by a composite material of quantum dots and carbon dots. Comparative examples 4 to 6 are for illustrating the process of catalytically oxidizing cyclohexane using a catalytic material different from that of the present disclosure.
In the following examples and comparative examples, the oxidation products were analyzed by gas chromatography (GC: agilent, 7890A) and gas chromatography-mass spectrometer (GC-MS: thermo Fisher Trace ISQ). Conditions for gas chromatography: nitrogen carrier gas, temperature programmed at 140K: 60 ℃,1 minute, 15 ℃/minute, 180 ℃,15 minutes; split ratio, 10:1; the injection port temperature is 300 ℃; detector temperature, 300 ℃. On the basis, the following formulas are respectively adopted to calculate the conversion rate of the raw materials and the selectivity of the target product:
cyclohexane conversion% = (molar amount of cyclohexane added before reaction-molar amount of cyclohexane remaining after reaction)/molar amount of cyclohexane added before reaction × 100%;
cyclohexanol selectivity% = (molar amount of cyclohexanol produced after reaction)/molar amount of cyclohexane added before reaction × 100%.
Example 9
50mg of the composite particles A1 as a catalyst and 10mL of cyclohexane were charged into a 250mL reaction vessel, followed by addition of 30% by weight aqueous hydrogen peroxide (molar ratio of hydrogen peroxide to cyclooctene: 2: 1) and sealing, stirring the mixture at 60 ℃ under 0.2MPa for reaction for 48 hours, cooling, pressure-releasing sampling, centrifuging and filtering to separate the catalyst, and analyzing the oxidation products, the results are shown in Table 2.
Examples 10 to 12
Cyclohexane was catalytically oxidized by the method of example 1, except that the same amount of the composite particles A2 to A4 was used instead of A1, respectively. The results of the oxidation products are shown in Table 2.
Example 13
60mg of composite particles A1 as a catalyst and 10mL of cyclohexane were charged into a 250mL reaction vessel, followed by addition of 30% by weight aqueous hydrogen peroxide (molar ratio of hydrogen peroxide to cyclooctene is 4: 1), sealing, stirring the mixture at 60 ℃ for 8 hours at 0.2MPa, cooling, pressure-releasing sampling, centrifuging and filtering to separate the catalyst, and analyzing the oxidation product results as shown in Table 2.
Example 14
20mg of the composite particles A1 as a catalyst and 10mL of cyclohexane were charged into a 250mL reaction vessel, followed by addition of 30% by weight aqueous hydrogen peroxide (molar ratio of hydrogen peroxide to cyclooctene was 2: 1), sealing, stirring the mixture at 60 ℃ under 0.2MPa for 8 hours, cooling, pressure-releasing sampling, centrifuging and filtering to separate the catalyst, and analyzing the oxidation products, the results are shown in Table 2.
Example 15
80mg of the composite particles A1 as a catalyst and 10mL of cyclohexane were charged into a 250mL reaction vessel, followed by addition of 30% by weight aqueous hydrogen peroxide (molar ratio of hydrogen peroxide to cyclooctene was 2: 1), sealing, stirring the mixture at 60 ℃ under 0.2MPa for 8 hours, cooling, pressure-releasing sampling, centrifuging and filtering to separate the catalyst, and analyzing the oxidation products, the results are shown in Table 2.
Example 16
50mg of the composite particles A1 as a catalyst were charged in a fixed bed reactor, and cyclohexane and 30 wt% of peroxide were addedFeeding the hydrogen water solution into the reactor, wherein the weight hourly space velocity of the cyclohexane is 5h -1 The results of the analysis of the oxidation products after 8 hours of reaction at 80 ℃ and 2MPa are shown in Table 2.
Comparative example 4
Cyclohexane was catalytically oxidized by the method of example 9, except that the same amount of D1 (BiVO) was used 4 QDs) replaces the composite particle A1. The results of the oxidation products are shown in Table 2.
Comparative example 5
Cyclohexane was catalytically oxidized according to the method of example 9, except that the same amount of carbon dots CDs was used instead of the composite particles A1. The results of the oxidation product analysis are shown in Table 2.
Comparative example 6
Cyclohexane was catalytically oxidized according to the method of example 9, except that the composite particles A1 were not used, i.e., the reaction was carried out without a catalyst. The results of the oxidation products are shown in Table 2.
TABLE 2
| Sources of catalyst | Cyclohexane conversion% | Cyclohexanol selectivity% |
| Example 9 | 15 | 92 |
| Example 10 | 13 | 89 |
| Example 11 | 11 | 87 |
| Example 12 | 10 | 85 |
| Example 13 | 14 | 91 |
| Example 14 | 12 | 88 |
| Example 15 | 11 | 86 |
| Example 16 | 15 | 91 |
| Comparative example 4 | 4 | 56 |
| Comparative example 5 | 9 | 71 |
| Comparative example 6 | 6 | 42 |
As can be seen from Table 2, the use of a catalyst containing BiVO 4 The composite material of quantum dots and carbon dots can be used as a catalyst under mild conditionsThe selective oxidation of cyclohexane is realized, and the conversion rate of raw materials and the selectivity of target products are higher.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure as long as it does not depart from the gist of the present disclosure.
Claims (21)
1. A process for the catalytic oxidation of a cyclic hydrocarbon, the process comprising: contacting a cyclic hydrocarbon with an oxidant in the presence of a catalyst to perform an oxidation reaction, wherein the catalyst contains BiVO 4 A composite of quantum dots and carbon dots;
the BiVO is based on the total weight of the composite material 4 The content of the quantum dots is 20 to 75 wt%, and the content of the carbon dots is 25 to 80 wt%;
the preparation steps of the composite material comprise:
(1) Respectively providing a solution A and a solution B, wherein the solution A is a solution containing a soluble anionic surfactant and a soluble salt of metal Bi, and the solution B is a solution containing a compound of metal V;
(2) Mixing the solution A and the solution B obtained in the step (1) under the condition of stirring to obtain a mixture;
(3) Carrying out hydrothermal reaction on the mixture obtained in the step (2) to obtain a hydrothermal reaction product;
(4) Uniformly mixing the hydrothermal reaction product obtained in the step (3) with the carbon dots, collecting a solid product, washing and drying;
the conditions of the oxidation reaction are as follows: the temperature is 50 to 100 ℃; the time is 4 to 72h; the pressure is 0 to 20MPa.
2. The method of claim 1, wherein the BiVO is based on the total weight of the composite material 4 The content of the quantum dots is 30 to 70 weight percent; the content of the carbon dots is 30 to 70 wt%.
3. The method of claim 1, wherein the carbon dots are graphene quantum dots, carbon nanodots, or polymer dots.
4. The method of claim 1, wherein the particle size of the composite material is 2 to 15nm.
5. The method of claim 4, wherein the particle size of the composite material is 3 to 12nm.
6. The method of claim 5, wherein the particle size of the composite material is 5 to 10nm.
7. The process according to claim 1, wherein in step (1), the molar ratio of the compound of metal V, the soluble anionic surfactant and the soluble salt of metal Bi is (0.5 to 3): (0.5 to 5): 1;
the soluble salt of the metal Bi is bismuth chloride, bismuth nitrate or bismuth sulfate; the soluble anionic surfactant is sodium oleate, alkyl sodium sulfonate, alkyl aryl sodium sulfonate, alkyl sodium sulfate or secondary alkyl sodium sulfate; the compound of the metal V is vanadate or vanadate.
8. The process according to claim 7, wherein the molar ratio of the compound of metal V, the soluble anionic surfactant and the soluble salt of metal Bi is (1 to 3): (2 to 4): 1.
9. the method of claim 1, wherein in step (2), the agitation conditions comprise: the stirring speed is 100 to 5000 r/min, and the stirring time is 0.5 to 6h.
10. The method of claim 9, wherein the agitation conditions comprise: the stirring speed is 800 to 2000 rpm, and the time is 1 to 4h.
11. The method of claim 1, wherein in step (3), the hydrothermal reaction comprises: carrying out a first hydrothermal reaction on the mixture at 100-200 ℃ for 1-48h, and then carrying out a second hydrothermal reaction at 160-250 ℃ for 1-24h.
12. The method of claim 1, wherein in step (4), the weight ratio of the carbon points to the hydrothermal reaction product is 1: (0.2 to 10);
the mixing is carried out under agitation conditions comprising: the stirring speed is 100 to 5000 r/min, and the time is 0.1 to 12h;
the drying conditions include: the temperature is 20 to 150 ℃.
13. The method of claim 12, wherein in step (4), the weight ratio of the carbon points to the hydrothermal reaction product is 1: (0.5 to 5).
14. The method according to claim 1, wherein the oxidation reaction is carried out in a slurry bed reactor, and the amount of the catalyst is 20 to 100mg based on 10mL of the cyclic hydrocarbon;
or the oxidation reaction is carried out in a fixed bed reactor, and the weight hourly space velocity of the cyclic hydrocarbon is 0.01 to 100h -1 。
15. The method according to claim 14, wherein the amount of the catalyst is 40 to 60mg based on 10mL of the cyclic hydrocarbon;
or the weight hourly space velocity of the cyclic hydrocarbon is 0.1 to 10h -1 。
16. The method of claim 1, wherein the molar ratio of the cyclic hydrocarbon to the oxidant is 1: (0.1 to 10);
the oxidant is hydrogen peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, ethylbenzene hydroperoxide or propionic acid peroxide.
17. The method of claim 16, wherein the molar ratio of the cyclic hydrocarbon to the oxidant is 1: (0.2 to 5);
the oxidant is hydrogen peroxide.
18. The method of claim 1, wherein the cyclic hydrocarbon comprises a cycloalkene and a cycloalkane;
the cycloolefin is one selected from C3-C8 cyclomonoolefin and C6-C8 cyclodiolefin;
the cycloalkane is one selected from C3-C8 cycloalkanes.
19. The method of claim 18, wherein the cyclic olefin is one selected from the group consisting of C3-C8 cyclic monoolefins;
the cycloalkane is one selected from cyclohexane, cyclopentane, alkyl substituted cyclohexane, alkyl substituted cyclopentane, halogen substituted cyclohexane or halogen substituted cyclopentane.
20. The process of claim 19, wherein the cyclic olefin is cyclooctene; the cycloalkane is cyclohexane.
21. The method of claim 1, wherein the oxidation reaction conditions are: the temperature is 60 to 80 ℃; the time is 6 to 48h; the pressure is 0 to 10MPa.
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